Analytic potential energy surfaces and their couplings for the electronically nonadiabatic chemical processes Na(3p)+H2→Na(3s)+H2 and Na(3p)+H2→NaH+H

摘要: High-level ab initio electronic structure calculations are presented for the ground and first excited state of NaH2 system. These include full configuration interaction (FCI) theory, second-order Mo/ller–Plesset perturbation (MP2) coupled cluster (CC) theory at a wide range geometries including those near conical intersection between state, points in excited-state potential energy well (exciplex), long-range van der Waals wells, regions where is dominated by forces. A 2×2 diabatic matrix function fit to high-level points. Special attention paid form that coupling should take method used this coupling. Long-range multipole dispersion forces, quadrupole–quadrupole interaction, included diagonal elements matrix. The its eigenvalues are...